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A new model for characterizing the free volume of a glassy polymer—gas systems is proposed. An improved method for the calculation of occupied volume per monomer unit was developed within the limits of this model. The model assumptions, error estimates and algorithm efficiencies are described. Using the example of polyvinyltrimethylsilane, it is shown that linear dependences of logarithms of the diffusion and the permeability coefficients on specific accessible volume for inert gases exist.

Methods for the calculation of occupied volumes in glassy polymers: The lattice integration and the monte carlo methods